End group functionalization agents for polydiene

ABSTRACT

The present invention relates to a modified polymer having the structure of Formula (I) and Formula (IV): 
                         
wherein A,
 
                         
R 1 , R 2 , R 3 , a, and n are as described herein and
 
                         
wherein
 
                         
R, R′, R″, x, and k are as described herein and methods for preparation thereof. The present invention also relates to a compound having the structure of Formula (II):
 
                         
wherein A, R 1 , R 2 , R 3 , a, and n are as described herein. The present invention also relates to a process for polymerizing unsaturated hydrocarbon monomers.

This application claims the priority benefit of U.S. Provisional PatentApplication Ser. No. 62/574,963, filed Oct. 20, 2017, which is herebyincorporated by reference in its entirety.

FIELD OF THE INVENTION

The present invention relates to an end group functionalization agentsfor polydiene.

BACKGROUND OF THE INVENTION

Since fuel economies and the need to preserve the environment havebecome priorities, the tire industry has been challenged to design tiresthat have improved rolling resistance, which contributes to better fuelefficiency. Attempts to improve rolling resistance have includedalternate tire designs and the use of rubber that has less hysteresisloss.

Tires are composed of a mixture of natural rubber, syntheticpolybutadiene rubber, filler, and other organic and inorganic materials.The dispersion of the filler, typically either carbon black or silica,in the rubber affects the tire's properties. These properties includethe rolling resistance, the wear resistance, and the tensile strength.

As for 1,3-butadiene polymerization, neodymium-based catalyst has alsodrawn particular interest since it gives a higher cis microstructurethan any other catalysts such as Li-, Na-, Ti-, Co- and Ni-catalysts do,and exhibits pseudo-living character which is a very rare case inZiegler-Natta catalyst reactions. Nd-polybutadiene also shows highabrasion resistance, low heat build-up, and high resilience, which arevery demanded properties for tire, golf-ball as well as high impactpolystyrene (HIPS) applications.

The present invention is directed to overcoming deficiencies in the art.

SUMMARY OF THE INVENTION

One aspect of the present invention relates to a modified polymer havingthe structure of Formula (I):

wherein

is a polymer;

A is selected from the group consisting of

alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, arylene, and

wherein C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, and arylenecan be optionally substituted from 1 to 4 times with a substituentindependently selected from the group consisting of H, halogen, C₁₋₆alkyl, and —NR⁷R⁸;

is a point of attachment of A to

group;

R¹ is C₁₋₆ alkyl;

R² is H or C₁₋₆ alkyl;

R³ is H or C₁₋₆ alkyl;

R⁴ is C₁₋₆ alkyl;

R⁵ is H or C₁₋₆ alkyl;

R⁶ is H or C₁₋₆ alkyl;

R⁷ is H or C₁₋₆ alkyl;

R⁸ is H or C₁₋₆ alkyl;

R⁹ is C₁₋₆ alkyl;

R¹⁰ is C₁₋₆ alkyl;

X¹ is C₁₋₆ alkylene;

X² is C₁₋₁₅ alkylene;

Y is O or N;

Z is H, R⁹, or Si(R¹⁰)₃;

a is 0 to 2;

b is 1 or 2; and

n is 1 to 3.

Another aspect of the present invention relates to a compound having thestructure of Formula (II):

wherein

A is selected from the group consisting of

C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, arylene, and

wherein C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, and arylenecan be optionally substituted from 1 to 4 times with a substituentindependently selected from the group consisting of H, halogen, C₁₋₆alkyl, and —NR⁷R⁸;

is a point of attachment of A to

group;

R¹ is C₁₋₆ alkyl;

R² is H or C₁₋₆ alkyl;

R³ is H or C₁₋₆ alkyl;

R⁴ is C₁₋₆ alkyl;

R⁵ is H or C₁₋₆ alkyl;

R⁶ is H or C₁₋₆ alkyl;

R⁷ is H or C₁₋₆ alkyl;

R⁸ is H or C₁₋₆ alkyl;

R⁹ is C₁₋₆ alkyl;

R¹⁰ is C₁₋₆ alkyl;

X¹ is C₁₋₆ alkylene;

X² is C₁₋₁₅ alkyene;

Y is O or N;

Z is H, R⁹, or Si(R¹⁰)₃;

a is 0 to 2;

b is 1 or 2;

n is 1 to 3; and

wherein 1) if a is 0; R¹ and R³ are Et, then A cannot be —Si(OEt)₃,n-Bu, i-Pr, t-Bu, or Ph, 2) if a is 0; R¹ and R³ are Me, then A cannotbe C₂₋₈ alkylene.

Yet another aspect of the present invention relates to a process forpolymerizing unsaturated hydrocarbon monomers. This process includes:providing unsaturated hydrocarbon monomers; providing a compound ofFormula (II):

wherein

A is selected from the group consisting of

C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, arylene, and

wherein C₁₋₁₅ alky, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, and arylenecan be optionally substituted from 1 to 4 times with a substituentindependently selected from the group consisting of H, halogen, C₁₋₆alkyl, and —NR⁷R⁸;

is a point of attachment of A to

group;

R¹ is C₁₋₆ alkyl;

R² is H or C₁₋₆ alkyl;

R³ is H or C₁₋₆ alkyl;

R⁴ is C₁₋₆ alkyl;

R⁵ is H or C₁₋₆ alkyl;

R⁶ is H or C₁₋₆ alkyl;

R⁷ is H or C₁₋₆ alkyl;

R⁸ is H or C₁₋₆ alkyl;

R⁹ is C₁₋₆ alkyl;

R¹⁰ is C₁₋₆ alkyl;

X¹ is C₁₋₆ alkylene;

X² is C₁₋₁₅ alkyene;

Y is O or N;

Z is H, R⁹, or Si(R¹⁰)₃;

a is 0 to 2;

b is 1 or 2;

n is 1 to 3; and

providing a catalyst selected from the group consisting of: (1) amixture of (A) a compound of Formula M¹A¹ ₃; (B) a halogen containingcompound; and (C) an organometallic compound, wherein M¹ is a lanthanidemetal; A¹ is C₈₋₂₀ carboxylate; (2) a mixture of (A) a compound ofFormula M²(HA²)A² ₃; (B) a halogen containing compound; and (C) anorganometallic compound, wherein M² is a lanthanide metal; A² is C₈₋₂₀carboxylate; (3) a compound of Formula Li-Alk, wherein Alk is C₁₋₆alkyl; and (4) a compound of Formula (III): MC(SiHAlk₂)₃(R¹¹)₂ (III),wherein M is a lanthanide or a transition metal; Alk is C₁₋₆ alkyl; R¹¹is halide, bis(oxazolinato), carboxylate, acetyl acetonate, amidate,alkoxide, amide, BR¹² ₄, AlR¹² ₄, or alkyl aluminate; R¹² isindependently selected at each occurrence thereof from the groupconsisting of H, C₆F₅, phenyl, and C₁₋₆ alkyl; and

polymerizing the unsaturated hydrocarbon monomers in the presence of thecatalyst and the compound of Formula (II) under conditions effective toproduce the modified polymer.

Another aspect of the present invention relates to a process forproducing a modified polymer. This process includes: providing apolymer; providing a compound of Formula (II):

wherein

A is selected from the group consisting of

C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, arylene, and

wherein C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, and arylenecan be optionally substituted from 1 to 4 times with a substituentindependently selected from the group consisting of H, halogen, C₁₋₆alkyl, and —NR⁷R⁸;

is a point of attachment of A to

group;

R¹ is C₁₋₆ alkyl;

R² is H or C₁₋₆ alkyl;

R³ is H or C₁₋₆ alkyl;

R⁴ is C₁₋₆ alkyl;

R⁵ is H or C₁₋₆ alkyl;

R⁶ is H or C₁₋₆ alkyl;

R⁷ is H or C₁₋₆ alkyl;

R⁸ is H or C₁₋₆ alkyl;

R⁹ is C₁₋₆ alkyl;

R¹⁰ is C₁₋₆ alkyl;

X¹ is C₁₋₆ alkylene;

X² is C₁₋₁₅ alkyene;

Y is O or N;

Z is H, R⁹, or Si(R¹⁰)₃;

a is 0 to 2;

b is 1 or 2;

n is 1 to 3; and

reacting the polymer with the compound of Formula (II) under conditionseffective to produce the modified polymer.

Yet another aspect of the present invention relates to a modifiedpolymer having the structure of Formula (IV):

wherein

each

indicates a bond with cis and/or trans geometric isomerism;

is a polymer of formula

R is H or C₁₋₆ alkyl;

R′ is selected from the group consisting of H, C₁₋₆ alkyl, —OC₁₋₆ alkyl;—NR^(a)R^(b);

R″ is H or C₁₋₆ alkyl;

R^(a) is H or C₁₋₆ alkyl;

R^(b) is H or C₁₋₆ alkyl;

W is a repeating unit of the polymer;

m is 1000 to 55000;

k is 1 or 500; and

x is 0 to 3.

A further aspect of the present invention relates to a process forpolymerizing unsaturated hydrocarbon monomers. This process includes:

providing unsaturated hydrocarbon monomers;

providing a compound of Formula (V)

wherein

R is H or C₁₋₆ alkyl;

R′ is selected from the group consisting of H, C₁₋₆ alkyl, —OC₁₋₆ alkyl;—NR^(a)R^(b);

R″ is H or C₁₋₆ alkyl;

R^(a) is H or C₁₋₆ alkyl;

R^(b) is H or C₁₋₆ alkyl; and

x is 0 to 3; and

providing a catalyst selected from the group consisting of: (1) amixture of (A) a compound of Formula M¹A¹ ₃; (B) a halogen containingcompound; and (C) an organometallic compound, wherein M¹ is a lanthanidemetal; A¹ is C₈₋₂₀ carboxylate; (2) a mixture of (A) a compound ofFormula M²(HA²)A² ₃; (B) a halogen containing compound; and (C) anorganometallic compound, wherein M² is a lanthanide metal; A² is C₈₋₂₀carboxylate; (3) a compound of Formula Li-Alk, wherein Alk is C₁₋₆alkyl; and (4) a compound of Formula (III): MC(SiHAlk₂)₃(R¹¹)₂ (III),wherein M is a lanthanide or a transition metal; Alk is C₁₋₆ alkyl; R¹¹is halide, bis(oxazolinato), carboxylate, acetyl acetonate, amidate,alkoxide, amide, BR¹² ₄, AlR¹² ₄, or alkyl aluminate; R¹² isindependently selected at each occurrence thereof from the groupconsisting of H, C₆F₅, phenyl, and C₁₋₆ alkyl; and

polymerizing the unsaturated hydrocarbon monomers in the presence of thecatalyst and the compound of Formula (V) under conditions effective toproduce the modified polymer.

Yet another aspect of the present invention relates to a process forproducing a modified polymer. This process includes:

providing a polymer;

providing a compound of Formula (V):

wherein

R is H or C₁₋₆ alkyl;

R′ is selected from the group consisting of H, C₁₋₆ alkyl, —OC₁₋₆ alkyl;—NR^(a)R^(b);

R″ is H or C₁₋₆ alkyl;

R^(a) is H or C₁₋₆ alkyl;

R^(b) is H or C₁₋₆ alkyl;

x is 0 to 3; and

reacting the polymer with the compound of Formula (V) under conditionseffective to produce the modified polymer.

Tires are composed of a mixture of natural rubber, syntheticpolybutadiene rubber produced from neodymium catalysis, filler, andother organic and inorganic materials. The dispersion of the filler,typically either carbon black or silica, in the rubber affects thetire's properties. These properties include the rolling resistance, thewear resistance, and the tensile strength. Interactions between polymerchain ends and filler may be enhanced through chain endfunctionalization reactions.

The present application describes a new class of functionalizationagents that can be added to neodymium-catalyzed butadienepolymerizations to give end-group functionalizations that improve theproperties of poly butadiene rubber in compound formulations whencompared to current commercial standard formulations. These organicfunctionalization groups attach to polymer chain ends through activepolymerization sites through interaction with an alkyne group.Functional groups such as triethoxysilyl groups bonded to the alkynewere incorporated into chain ends, and these are believed to interactwith silica filler to provide formulations with improved fuel efficiencyand wet skid resistance.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the results of gel permeating chromatography for polymersproduced in Examples 4 and 5.

FIG. 2 shows a DOSY NMR of isolated product.

FIG. 3 shows ¹H NMR spectra of polyisoprene synthesized from catalysisusing NdV₄, 5 TIBA, 2.5 DIBAl—H, and 1,5 DIBAl—Cl, quenched with(EtO)₃SiCCSi(OEt)₃.

FIG. 4 shows ¹H NMR spectra for the (EtO)₃SiCCSi(OEt)₃ derivatizedpolyisoprene.

FIG. 5 shows ¹H NMR analysis of reaction progress for the reduction of1,4-dichloro-2-dimethyltertbutoxysilyl-2-butene with zinc

FIG. 6 shows ¹H NMR of 2-Me₂SiNMe₂-1,3-butadiene partially decomposed inbenzene-d₆.

FIG. 7 shows ¹H NMR of the isolated copolymer material.

FIG. 8 shows ²⁹Si{¹H} HMBC NMR of isolated co-polymer material.

FIG. 9 shows DOSY NMR of isolated co-polymer material.

FIG. 10 shows ¹H NMR of isolate co-polymer material.

FIG. 11 shows ²⁹Si {¹H} HMBC NMIR of isolated co-polymer material.

FIG. 12 shows DOSY NMR of isolated co-polymer material.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a modified polymer having the structureof Formula (I):

wherein

is a polymer;

A is selected from the group consisting of

C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, arylene, and

wherein C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, and arylenecan be optionally substituted from 1 to 4 times with a substituentindependently selected from the group consisting of H, halogen, C₁₋₆alkyl, and —NR⁷R⁸;

is a point of attachment of A to

group;

R¹ is C₁₋₆ alkyl;

R² is H or C₁₋₆ alkyl;

R³ is H or C₁₋₆ alkyl;

R⁴ is C₁₋₆ alkyl;

R⁵ is H or C₁₋₆ alkyl;

R⁶ is H or C₁₋₆ alkyl;

R⁷ is H or C₁₋₆ alkyl;

R⁸ is H or C₁₋₆ alkyl;

R⁹ is C₁₋₆ alkyl;

R¹⁰ is C₁₋₆ alkyl;

X¹ is C₁₋₆ alkylene;

X² is C₁₋₁₅ alkylene;

Y is O or N;

Z is H, R⁹, or Si(R¹⁰)₃;

a is 0 to 2;

b is 1 or 2; and

n is 1 to 3.

As used above, and throughout the description herein, the followingterms, unless otherwise indicated, shall be understood to have thefollowing meanings. If not defined otherwise herein, all technical andscientific terms used herein have the same meaning as is commonlyunderstood by one of ordinary skill in the art to which this technologybelongs. In the event that there is a plurality of definitions for aterm herein, those in this section prevail unless stated otherwise.

The term “lanthanide” or “lanthanide metal atom” refers to the elementwith atomic numbers 57 to 71. Lanthanides include La, Ce, Pr, Nd, Pm,Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

The term “transition metal” refers to an element whose atom has anincomplete d sub-shell, or which can give rise to cations with anincomplete d sub-shell. Transition metals include Sc, Ti, V, Cr, Mn, Fe,Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re,Os, Ir, Pt, Au, Hg, Ac, Rf, and Ha.

The term “alkyl” refers to an aliphatic hydrocarbon group which may bestraight or branched having about 1 to about 15 carbon atoms in thechain. Branched means that one or more lower alkyl groups such asmethyl, ethyl, or propyl are attached to a linear alkyl chain. Exemplaryalkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl,t-butyl, n-pentyl, and 3-pentyl.

The term “alkylene” refers to a group obtained by removal of a hydrogenatom from an alkyl group. Non-limiting examples of alkylene includemethylene and ethylene.

The term “cycloalkyl” refers to a non-aromatic, saturated orunsaturated, mono- or multi-cyclic ring system of about 3 to about 8carbon atoms, or of about 5 to about 7 carbon atoms, and which mayinclude at least one double bond. Exemplary cycloalkyl groups include,without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclophenyl,anti-bicyclopropane, and syn-tricyclopropane.

The term “aryl” refers to an aromatic monocyclic or multi-cyclic(polycyclic) ring system of 6 to about 19 carbon atoms, or of 6 to about10 carbon atoms, and includes arylalkyl groups. The ring system of thearyl group may be optionally substituted. Representative aryl groupsinclude, but are not limited to, groups such as phenyl, naphthyl,azulenyl, phenanthrenyl, anthracenyl, fluorenyl, pyrenyl, triphenylenyl,chrysenyl, and naphthacenyl.

The term “alkoxy” means groups of from 1 to 15 carbon atoms of astraight, branched, or cyclic configuration and combinations thereofattached to the parent structure through an oxygen. Examples includemethoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, cyclohexyloxy, andthe like.

The term “arylalkyl” means an alkyl residue attached to an aryl ring.Examples are benzyl, phenethyl, and the like.

The term “monocyclic” used herein indicates a molecular structure havingone ring.

The term “polycyclic” or “multi-cyclic” used herein indicates amolecular structure having two or more rings, including, but not limitedto, fused, bridged, or spiro rings.

The term “arylene” refers to a group obtained by removal of a hydrogenatom from an aryl group. Non-limiting examples of arylene includephenylene and naphthylene.

The term “halide” refers to a halogen atom bearing a negative charge.

The term “halogen” means fluoro, chloro, bromo, or iodo.

The term “bis(oxazolinato)” or “BOX” refers to compounds containing twooxazoline rings. Exemplary bis(oxazolinato) ligands are shown below.

The term “alkyl aluminate” refers to compounds represented by theformula [Al[O_(m)(R¹O)_(n)R² _(o)]_(n)]⁻, wherein R¹O is alkyloxide; R²is alkyl; the sum of m/2+n+o is 4; and n is 1 to 4.

The term “carboxylate” refers to a conjugate base of a carboxylic acid,RCOO⁻ (where R is the organic substituent).

The term “acetyl acetonate” refers to the enol form of acetylacetone.

The term “amidate” refers to a carboximate of the type RCONR′⁻, as theconjugate base of an amide RCONHR′ (where R and R′ are organicsubstituents).

The term “alkoxide” refers to the conjugate base of an alcohol, RO⁻(where R is the organic substituent).

The term “amide” refers to a conjugate base of ammonia (the anion H₂N⁻)or of an organic amine (an anion R₂N⁻).

The term “phenyl” means a phenyl group as shown below:

The term “optionally substituted” is used to indicate that a group mayhave a substituent at each substitutable atom of the group (includingmore than one substituent on a single atom), provided that thedesignated atom's normal valency is not exceeded and the identity ofeach substituent is independent of the others. Up to three H atoms ineach residue are replaced with alkyl, halogen, haloalkyl, hydroxy,loweralkoxy, carboxy, carboalkoxy (also referred to as alkoxycarbonyl),carboxamido (also referred to as alkylaminocarbonyl), cyano, carbonyl,nitro, amino, alkylamino, dialkylamino, mercapto, alkylthio, sulfoxide,sulfone, acylamino, amidino, phenyl, benzyl, heteroaryl, phenoxy,benzyloxy, or heteroaryloxy. “Unsubstituted” atoms bear all of thehydrogen atoms dictated by their valency. When a substituent is keto(i.e., =0), then two hydrogens on the atom are replaced. Combinations ofsubstituents and/or variables are permissible only if such combinationsresult in stable compounds; by “stable compound” or “stable structure”is meant a compound that is sufficiently robust to survive isolation toa useful degree of purity from a reaction mixture, and formulation intoan efficacious therapeutic agent.

In one embodiment, the modified polymer has the structure of Formula(Ia):

wherein

A is selected from the group consisting of

C₁₋₁₅ alkyl, C₃₋₈ cycloalkyl, and aryl, wherein C₁₋₁₅ alkyl, C₃₋₈cycloalkyl, and aryl can be optionally substituted from 1 to 4 timeswith a substituent independently selected from the group consisting ofH, halogen, C₁₋₆ alkyl, and —NR⁷R⁸.

In another embodiment, the modified polymer has the structure:

In a further embodiment, the modified polymer has the structure:

The term “polymer”,

or

refers to any suitable polymer. In one embodiment polymer

is prepared by polymerization of any unsaturated hydrocarbon monomer ormonomers. In another embodiment polymer

is prepared by polymerization of any unsaturated hydrocarbon monomer ormonomers.

Preferred monomers that can be used according to prepare polymer

or

according to the present invention include olefins, polyenes, and vinylaromatic hydrocarbons.

Polyenes, particularly dienes and trienes (e.g., myrcene) can beemployed in accordance with the present invention. Illustrative polyenesinclude C₄-C₃₀ dienes, preferably C₄-C₁₂ dienes. Preferred among theseare conjugated dienes such as, but not limited to, 1,3-butadiene,1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene,2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene,2-methyl-1,3-butadiene, 2-methyl-1,3-pentadiene,3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2,4-hexadiene, and thelike.

Examples of olefins that can be employed according to the presentinvention include C₂-C₃₀ straight chain or branched α-olefins such asethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene,4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, and the like, as wellas C₃-C₃₀ cyclo-olefins such as cyclopentene, cycloheptene, norbornene,5-methyl-2-norbornene, and tetra-cyclododecene.

Vinyl aromatic hydrocarbons which may be used according to the presentinvention include vinyl aryl compounds such as, styrene, variousalkyl-substituted styrenes, alkoxysubstituted styrenes, 2-vinylpyridine,4-vinylpyridine, vinylnaphthalene, alkyl-substituted vinyl napthalenesand the like.

One embodiment relates to the modified polymer of the present inventionwhere the polymer

has 1,4-cis content of 15 to 99%, or of 20 to 99%, or of 25 to 99%, orof 30 to 99%, or of 35 to 99%, or of 40 to 99%, or of 45 to 99%, or of50 to 99%, or of 55 to 99%, or of 60 to 99%, or of 65 to 99%, or of 70to 99%, or of 75 to 99%, or of 80 to 99%, or of 85 to 99%, or of 90 to99%, or of 95% to 99%.

Another embodiment relates to the modified polymer of the presentinvention where the polymer

has 1,4-cis content of 15 to 20%, or of 20 to 25%, or of 25 to 30%, orof 30 to 35%, or of 35 to 40%, or of 40 to 45%, or of 45 to 50%, or of50 to 55%, or of 55 to 60%, or of 60 to 65%, or of 65 to 70%, or of 70to 75%, or of 75 to 80%, or of 80 to 85%, or of 85 to 90%, or of 90 to95%, or of 95% to 99%.

Yet another embodiment relates to the modified polymer of the presentinvention where the polymer

is a polymer of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene,1,3-pentadiene, 1,3-hexadiene, or myrcene. Another embodiment relates tothe modified polymer of the present invention where the polymer

is a polymer of isoprene.

Another aspect of the present invention relates to a compound having thestructure of Formula (II):

wherein

A is selected from the group consisting of

C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, arylene, and

wherein C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, and arylenecan be optionally substituted from 1 to 4 times with a substituentindependently selected from the group consisting of H, halogen, C₁₋₆alkyl, and —NR⁷R⁸;

is a point of attachment of A to

group;

R¹ is C₁₋₆ alkyl;

R² is H or C₁₋₆ alkyl;

R³ is H or C₁₋₆ alkyl;

R⁴ is C₁₋₆ alkyl;

R⁵ is H or C₁₋₆ alkyl;

R⁶ is H or C₁₋₆ alkyl;

R⁷ is H or C₁₋₆ alkyl;

R⁸ is H or C₁₋₆ alkyl;

R⁹ is C₁₋₆ alkyl;

R¹⁰ is C₁₋₆ alkyl;

X¹ is C₁₋₆ alkylene;

X² is C₁₋₁₅ alkyene;

Y is O or N;

Z is H, R⁹, or Si(R¹⁰)₃;

a is 0 to 2;

b is 1 or 2;

n is 1 to 3; and

wherein 1) if a is 0; R¹ and R³ are Et, then A cannot be —Si(OEt)₃,n-Bu, i-Pr, t-Bu, or Ph, 2) if a is 0; R¹ and R³ are Me, then A cannotbe C₂₋₈ alkylene.

In one embodiment, the compound of Formula (II) has the Formula (IIa):

wherein

A is selected from the group consisting of

C₁₋₁₅ alkyl, C₃₋₈ cycloalkyl, and aryl, wherein C₁₋₁₅ alkyl, C₃₋₈cycloalkyl, and aryl can be optionally substituted from 1 to 4 timeswith a substituent independently selected from the group consisting ofH, halogen, C₁₋₆ alkyl, and —NHR⁷R⁸.

In one embodiment, the compound of Formula (IIa) has the followingstructure:

In another embodiment, the compound of Formula (IIa) has the followingstructure:

Another aspect of the present invention relates to a process forpolymerizing unsaturated hydrocarbon monomers. This process includes:providing unsaturated hydrocarbon monomers; providing a compound ofFormula (II):

wherein

A is selected from the group consisting of

C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, arylene, and

wherein C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, and arylenecan be optionally substituted from 1 to 4 times with a substituentindependently selected from the group consisting of H, halogen, C₁₋₆alkyl, and —NR⁷R⁸;

is a point of attachment of A to

group;

R¹ is C₁₋₆ alkyl;

R² is H or C₁₋₆ alkyl;

R³ is H or C₁₋₆ alkyl;

R⁴ is C₁₋₆ alkyl;

R⁵ is H or C₁₋₆ alkyl;

R⁶ is H or C₁₋₆ alkyl;

R⁷ is H or C₁₋₆ alkyl;

R⁸ is H or C₁₋₆ alkyl;

R⁹ is C₁₋₆ alkyl;

R¹⁰ is C₁₋₆ alkyl;

X¹ is C₁₋₆ alkylene;

X² is C₁₋₁₅ alkyene;

Y is O or N;

Z is H, R⁹, or Si(R¹⁰)₃;

a is 0 to 2;

b is 1 or 2;

n is 1 to 3; and

providing a catalyst selected from the group consisting of: (1) amixture of (A) a compound of Formula M¹A¹ ₃; (B) a halogen containingcompound; and (C) an organometallic compound, wherein M¹ is a lanthanidemetal; A¹ is C₈₋₂₀ carboxylate; (2) a mixture of (A) a compound ofFormula M²(HA²)A² ₃; (B) a halogen containing compound; and (C) anorganometallic compound, wherein M² is a lanthanide metal; A² is C₈₋₂₀carboxylate; (3) a compound of Formula Li-Alk, wherein Alk is C₁₋₆alkyl; and (4) a compound of Formula (III): MC(SiHAlk₂)₃(R¹¹)₂ (III),wherein M is a lanthanide or a transition metal; Alk is C₁₋₆ alkyl; R¹¹is halide, bis(oxazolinato), carboxylate, acetyl acetonate, amidate,alkoxide, amide, BR¹² ₄, AlR¹² ₄, or alkyl aluminate; R¹² isindependently selected at each occurrence thereof from the groupconsisting of H, C₆F₅, phenyl, and C₁₋₆ alkyl; and

polymerizing the unsaturated hydrocarbon monomers in the presence of thecatalyst and the compound of Formula (II) under conditions effective toproduce the modified polymer.

In one embodiment, the catalyst used in process for polymerizingunsaturated hydrocarbon monomers is a mixture of (A) a compound ofFormula M¹A¹ ₃; (B) a halogen containing compound; and (C) anorganometallic compound, wherein M¹ is a lanthanide metal; A¹ is C₈₋₂₀carboxylate.

Suitable halogen containing compounds include, but are not limited to,aluminum halogen compounds represented by Formula R^(a) _(n)AlX_(3-n),wherein R^(a) is hydrogen or an alkyl or aryl group containing 1 to 10carbon atoms, X is halogen, and n is an integer from 1 to 3; andinorganic or organic halogen compounds in which aluminum is completelysubstituted by boron, silicon, tin or titanium in the aluminum halogencompounds, wherein the halogen containing compounds are preferably alkylhalogen compounds containing 4 to 20 carbon atoms.

Suitable organometallic compounds include, but are not limited to, alkylaluminum compounds represented by AlR^(b) ₃; alkyl magnesium compoundsrepresented by MgR^(b) ₂; alkyl zinc compounds represented by ZnR^(b) ₂and alkyl lithium compounds represented by LiR^(b) wherein R^(b) ishydrogen or an alkyl, cycloalkyl, aryl, arylaklyl, or alkoxy groupcontaining 1 to 10 carbon atoms. Exemplary suitable organometalliccompounds include, without limitation, trimethyl aluminum, triethylaluminum, tripropyl aluminum, tributyl aluminum, triisobutyl aluminum,trihexyl aluminum, diisobutyl aluminum hydride, dibutyl magnesium,diethyl magnesium, dibutyl zinc, diethyl zinc, and n-butyl lithium.

In another embodiment, the catalyst used in the process for polymerizingunsaturated hydrocarbon monomers is a mixture of (A) a compound ofFormula M²(HA²)A² ₃; (B) a halogen containing compound; and (C) anorganometallic compound, wherein M² is a lanthanide metal; A² is C₈₋₂₀carboxylate.

In yet another embodiment, the catalyst is a compound of Formula Li-Alk,wherein Alk is C₁₋₆ alkyl.

In a further embodiment, the catalyst is a compound of Formula (III):MC(SiHAlk₂)₃(R¹¹)₂ (III), wherein M is a lanthanide or a transitionmetal; Alk is C₁₋₆ alkyl; R¹¹ is halide, bis(oxazolinato), carboxylate,acetyl acetonate, amidate, alkoxide, amide, BR¹² ₄, AlR¹² ₄, or alkylaluminate; R¹² is independently selected at each occurrence thereof fromthe group consisting of H, C₆F₅, phenyl, and C₁₋₆ alkyl.

The modified polymer, according to the present invention, can beprepared according to the Schemes 1-5 shown below.

Unsaturated hydrocarbon monomer or monomers (2) can be polymerized inthe presence of the compound (1) and catalyst (3). Reaction can becarried in a variety of solvents at room temperature or at elevatedtemperature. In some embodiments, the reaction can be carried out in thepresence of a halogen containing compound. In some embodiments, thereaction can be carried out in the presence of an organometalliccompound. The polymerization reaction can be terminated by usingreaction terminators.

The processes of this invention are used to polymerize any unsaturatedhydrocarbon monomer or monomers. Preferred monomers that can be usedaccording to the present invention include olefins, polyenes, and vinylaromatic hydrocarbons.

Polyenes, particularly dienes and trienes (e.g., myrcene) can beemployed in accordance with the present invention. Illustrative polyenesinclude C₄-C₃₀ dienes, preferably C₄-C₁₂ dienes. Preferred among theseare conjugated dienes such as, but not limited to, 1,3-butadiene,1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene,2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene,2-methyl-1,3-butadiene, 2-methyl-1,3-pentadiene,3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2,4-hexadiene, and thelike.

Examples of olefins that can be employed according to the presentinvention include C₂-C₃₀ straight chain or branched α-olefins such asethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene,4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, and the like, as wellas C₃-C₃₀ cyclo-olefins such as cyclopentene, cycloheptene, norbornene,5-methyl-2-norbornene, and tetra-cyclododecene.

Vinyl aromatic hydrocarbons which may be used according to the presentinvention include vinyl aryl compounds such as, styrene, variousalkyl-substituted styrenes, alkoxysubstituted styrenes, 2-vinylpyridine,4-vinylpyridine, vinylnaphthalene, alkyl-substituted vinyl napthalenesand the like.

One embodiment relates to the process of the present invention where theunsaturated hydrocarbon monomer is a 1,3-butadiene, isoprene,2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, or myrcene.In one embodiment, the monomer is isoprene.

Depending on the catalyst used for the polymerization, the modifiedpolymer of the present invention can be prepared with varying degrees of1,4-cis content.

One embodiment relates to the modified polymer of the present inventionhas 1,4-cis content of 15 to 99%, or of 20 to 99%, or of 25 to 99%, orof 30 to 99%, or of 35 to 99%, or of 40 to 99%, or of 45 to 99%, or of50 to 99%, or of 55 to 99%, or of 60 to 99%, or of 65 to 99%, or of 70to 99%, or of 75 to 99%, or of 80 to 99%, or of 85 to 99%, or of 90 to99%, or of 95% to 99%.

Another embodiment relates to the modified polymer of the presentinvention has 1,4-cis content of 15 to 20%, or of 20 to 25%, or of 25 to30%, or of 30 to 35%, or of 35 to 40%, or of 40 to 45%, or of 45 to 50%,or of 50 to 55%, or of 55 to 60%, or of 60 to 65%, or of 65 to 70%, orof 70 to 75%, or of 75 to 80%, or of 80 to 85%, or of 85 to 90%, or of90 to 95%, or of 95% to 99%.

Another embodiment relates to the modified polymer of the presentinvention has more than 90% 1,4-cis content.

The non-polar solvent used for the polymerization of unsaturatedhydrocarbon monomers should contain at least one or more aliphatichydrocarbons (e.g., butane, pentane, hexane, isopentane, heptane,octane, and isooctane); cycloaliphatic hydrocarbons (e.g., cyclopentane,methylcyclopentane, cyclohexane, methylcyclohexane, andethylcyclohexane); aromatic hydrocarbons (e.g., benzene, toluene,ethylbenzene, or xylene).

Another embodiment relates to the process of the present invention wherepolymerization is carried in a presence of a solvent. In one embodiment,the solvent is a non-polar solvent not reactive with the components ofthe catalyst system. Examples of suitable solvents include: aliphatichydrocarbons such as pentane, hexane, isopentane, heptane, octane andisooctane; cycloaliphatic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methyl cyclohexane and ethyl cyclohexane; andaromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene.Preferred non-polar solvents include cyclohexane, hexane, heptane, ortoluene.

The polymerization solvent, which can significantly affectpolymerization, is used after removal of oxygen and water.Polymerization is initiated in an inert atmosphere (preferably, underhigh-purity nitrogen atmosphere) and the polymerization temperature ispreferably carried out at room temperature to 100° C., more preferably40° C. to 80° C., most preferably 60° C. Under the appropriate catalystconditions, the polymerization can be carried out for 10 min to 10hours, preferably 30 min to 6 hours, most preferably two-hours.

The molar ratio of the unsaturated hydrocarbon monomer to the solvent is1:1 to 30:1, preferably 2:1 to 10:1.

Unsaturated hydrocarbon monomers can be added to the reaction mixture inone portion or gradually. When the unsaturated hydrocarbon monomer isgradually added to the reaction mixture, it may be allowed to react for10 min to 3 hours prior to addition of the next portion of theunsaturated hydrocarbon monomer. More preferably, this period can be 15min to 2 hours, most preferably 15 to 30 min.

The conversion of the unsaturated hydrocarbon monomers to the polymerunder the conditions described above is more than 50%, preferably morethan 80%, most preferably, more than 90%.

After polymerization is completed, known processes such as catalystinactivation treatment, catalyst removing treatment, and drying can beperformed if required. The polymerization can be completed byintroducing a reaction terminator and/or a stabilizer. The resultingpolybutadiene can be precipitated, for example, with methanol orethanol.

The reaction terminators that can be used according to the presentinvention include polyoxyethyleneglycolether organophosphate, methanol,ethanol, isopropanol, water, or carbon dioxide, organic acids such asoctanoic acid, decanoic acid and stearic acid, and the like.

The phenol stabilizers that can be used according to the presentinvention can be any of known phenol stabilizers having a phenolstructure. Examples are 2,6-di-t-butyl-p-cresol,2,6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-p-cresol,2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-p-cresol,2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol,2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol,2-isobutyl-4-ethyl-6-t-hexylphenol,2-cyclohexyl-4-n-butyl-6-isopropylphenol,2-t-butyl-6-(3′-t-butyl)-5′-methyl-2′hydroxybenzyl)-4-methylphenylacrylate,t-butylhydroquinone, 2,2′-methylenebis(4-methyl-6-t-butylphenol),4,4′-butylidenebis(3-methyl-6-t-butylphenol),4,4′-thiobis(3-methyl-6-t-butylphenol),2,2′-thiobis(4-methyl-6-t-butylphenol),4,4′-methylenebis(2,6-di-t-butylphenol),2,2′-methylenebis[6-(1-methylcyclohexyl)-p-cresol],2,2′-ethylidenebis(4,6-di-t-butylphenol),2,2′-butylidenebis(2-t-butyl-p-cresol),1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,triethyleneglycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],2,2-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],n-octadecyl-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate,N,N′-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide),3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethylester,1,3,5-tris(2,6-dimetyl-3-hydroxy-4-t-butylbenzyl)isocyanurate,1,3,5-tris[(3,5-di-t-butyl-4-hydroxyphenyl)propyonyloxyethyl]isocyanurate,2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine,tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane,bis(3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl)calcium,bis(3,5-di-t-butyl-4-hydroxybenzylphosphoric acid ethyl)nickel,N,N′-bis[3,5-di-t-butyl-4-hydroxyphenyl)propyonyl]hydrazine,2,2′-methylenebis(4-methyl-6-t-butylphenol)terephthalate,1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,3,9-bis[1,1-dimethyl-2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane,2,2-bis[4-{2-(3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy)}ethoxyphenyl]propane,and the like. Preferred stabilizer is 2,6-di-t-butyl-p-cresol.

Suitable catalysts of Formula (III) can be prepared as described in U.S.Pat. No. 9,856,337, which is hereby incorporated by reference in itsentirety.

In one embodiment, the catalyst comprises (A) a neodymium compound; (B)a halogen compound; and (C) an organometallic compound.

The modified polymer has a molecular weight below 4,000,000. Preferably,the modified polymer has a molecular weight below 3,500,000; themodified polymer has a molecular weight below 3,000,000; the modifiedpolymer has a molecular weight below 2,500,000; the modified polymer hasa molecular weight below 2,000,000; the modified polymer has a molecularweight below 1,500,000; the modified polymer has a molecular weightbelow 1,000,000; a molecular weight below 900,000; a molecular weightbelow 800,000; a molecular weight below 700,000; a molecular weightbelow 600,000; a molecular weight below 500,000.

The modified polymer has a molecular weight of 10,000 to 4,000,000.Preferably, the modified polymer has a molecular weight of 25,000 to3,500,000; a molecular weight of 50,000 to 3,500,000; a molecular weightof 50,000 to 3,000,000; a molecular weight of 75,000 to 3,000,000; amolecular weight of 100,000 to 3,000,000; a molecular weight of 100,000to 2,500,000; a molecular weight of 100,000 to 2,000,000; a molecularweight of 150,000 to 1,750,000; a molecular weight of 200,000 to1,700,000; a molecular weight of 250,000 to 1,600,000; a molecularweight of 300,000 to 1,500,000; a molecular weight of 400,000 to1,500,000; a molecular weight of 500,000 to 1,500,000; a molecularweight of 500,000 to 1,000,000.

In one embodiment, the modified polymer has a molecular weight of100,000 to 2,000,000.

In yet another embodiment, the modified polymer has a Mooney viscosityof 10 to 100.

Another aspect of the present invention relates to a process forproducing a modified polymer. This process includes: providing apolymer; providing a compound of Formula (II):

wherein

A is selected from the group consisting of

C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, arylene, and

wherein C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, and arylenecan be optionally substituted from 1 to 4 times with a substituentindependently selected from the group consisting of H, halogen, C₁₋₆alkyl, and —NR⁷R⁸;

is a point of attachment of A to

group;

R¹ is C₁₋₆ alkyl;

R² is H or C₁₋₆ alkyl;

R³ is H or C₁₋₆ alkyl;

R⁴ is C₁₋₆ alkyl;

R⁵ is H or C₁₋₆ alkyl;

R⁶ is H or C₁₋₆ alkyl;

R⁷ is H or C₁₋₆ alkyl;

R⁸ is H or C₁₋₆ alkyl;

R⁹ is C₁₋₆ alkyl;

R¹⁰ is C₁₋₆ alkyl;

X¹ is C₁₋₆ alkylene;

X² is C₁₋₁₅ alkyene;

Y is O or N;

Z is H, R⁹, or Si(R¹⁰)₃;

a is 0 to 2;

b is 1 or 2;

n is 1 to 3; and

reacting the polymer with the compound of Formula (II) under conditionseffective to produce the modified polymer.

Yet another aspect of the present invention relates to a modifiedpolymer having the structure of Formula (IV):

wherein

each

indicates a bond with cis and/or trans geometric isomerism;

is a polymer of formula

R is H or C₁₋₆ alkyl;

R′ is selected from the group consisting of H, C₁₋₆ alkyl, —OC₁₋₆ alkyl;—NR^(a)R^(b);

R″ is H or C₁₋₆ alkyl;

R^(a) is H or C₁₋₆ alkyl;

R^(b) is H or C₁₋₆ alkyl;

W is a repeating unit of the polymer;

m is 1000 to 55000;

k is 1 or 500; and

x is 0 to 3.

One embodiment relates to a modified polymer having the structure ofFormula (IVa):

In one embodiment n˜m.

In another embodiment n>>m.

One embodiment relates to the modified polymer of the present inventionwhere the polymer

has 1,4-cis content of 15 to 99%, or of 20 to 99%, or of 25 to 99%, orof 30 to 99%, or of 35 to 99%, or of 40 to 99%, or of 45 to 99%, or of50 to 99%, or of 55 to 99%, or of 60 to 99%, or of 65 to 99%, or of 70to 99%, or of 75 to 99%, or of 80 to 99%, or of 85 to 99%, or of 90 to99%, or of 95% to 99%.

Another embodiment relates to the modified polymer of the presentinvention where the polymer

has 1,4-cis content of 15 to 20%, or of 20 to 25%, or of 25 to 30%, orof 30 to 35%, or of 35 to 40%, or of 40 to 45%, or of 45 to 50%, or of50 to 55%, or of 55 to 60%, or of 60 to 65%, or of 65 to 70%, or of 70to 75%, or of 75 to 80%, or of 80 to 85%, or of 85 to 90%, or of 90 to95%, or of 95% to 99%.

Yet another embodiment relates to the modified polymer of the presentinvention where the polymer

is a polymer of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene,1,3-pentadiene, 1,3-hexadiene, or myrcene. Another embodiment relates tothe modified polymer of the present invention where the polymer

is a polymer of isoprene. Yet another embodiment relates to the modifiedpolymer of the present invention where the polymer

is a polymer of butadiene. A further embodiment relates to the modifiedpolymer of the present invention where the polymer

is a polymer of 1,3-butadiene.

A further aspect of the present invention relates to a process forpolymerizing unsaturated hydrocarbon monomers. This process includes:

providing unsaturated hydrocarbon monomers;

providing a compound of Formula (V):

wherein

R is H or C₁₋₆ alkyl;

R′ is selected from the group consisting of H, C₁₋₆ alkyl, —OC₁₋₆ alkyl;—NR^(a)R^(b);

R″ is H or C₁₋₆ alkyl;

R^(a) is H or C₁₋₆ alkyl;

R^(b) is H or C₁₋₆ alkyl; and

x is 0 to 3; and

providing a catalyst selected from the group consisting of: (1) amixture of (A) a compound of Formula M¹A¹ ₃; (B) a halogen containingcompound; and (C) an organometallic compound, wherein M¹ is a lanthanidemetal; A¹ is C₈₋₂₀ carboxylate; (2) a mixture of (A) a compound ofFormula M²(HA²)A² ₃; (B) a halogen containing compound; and (C) anorganometallic compound, wherein M² is a lanthanide metal; A² is C₈₋₂₀carboxylate; (3) a compound of Formula Li-Alk, wherein Alk is C₁₋₆alkyl; and (4) a compound of Formula (III): MC(SiHAlk₂)₃(R¹¹)₂ (III),wherein M is a lanthanide or a transition metal; Alk is C₁₋₆ alkyl; R¹¹is halide, bis(oxazolinato), carboxylate, acetyl acetonate, amidate,alkoxide, amide, BR¹² ₄, AlR¹² ₄, or alkyl aluminate; R¹² isindependently selected at each occurrence thereof from the groupconsisting of H, C₆F₅, phenyl, and C₁₋₆ alkyl; and

polymerizing the unsaturated hydrocarbon monomers in the presence of thecatalyst and the compound of Formula (V) under conditions effective toproduce the modified polymer.

The modified polymer has a molecular weight below 4,000,000. Preferably,the modified polymer has a molecular weight below 3,500,000; themodified polymer has a molecular weight below 3,000,000; the modifiedpolymer has a molecular weight below 2,500,000; the modified polymer hasa molecular weight below 2,000,000; the modified polymer has a molecularweight below 1,500,000; the modified polymer has a molecular weightbelow 1,000,000.

The modified polymer has a molecular weight of 10,000 to 4,000,000.Preferably, the modified polymer has a molecular weight of 25,000 to3,500,000; a molecular weight of 50,000 to 3,500,000; a molecular weightof 50,000 to 3,000,000; a molecular weight of 75,000 to 3,000,000; amolecular weight of 100,000 to 3,000,000; a molecular weight of 100,000to 2,500,000; a molecular weight of 100,000 to 2,000,000.

Yet another aspect of the present invention relates to a process forproducing a modified polymer. This process includes:

providing a polymer;

providing a compound of Formula (V):

wherein

R is H or C₁₋₆ alkyl;

R′ is selected from the group consisting of H, C₁₋₆ alkyl, —OC₁₋₆ alkyl;—NR^(a)R^(b);

R″ is H or C₁₋₆ alkyl;

R^(a) is H or C₁₋₆ alkyl;

R^(b) is H or C₁₋₆ alkyl;

x is 0 to 3; and

reacting the polymer with the compound of Formula (V) under conditionseffective to produce the modified polymer.

The modified polymer can also be prepared according to the Scheme 6shown below.

Reaction can be carried in a variety of solvents as described above andat room temperature or at elevated temperature.

The modified polymer can also be prepared according to the Scheme 7shown below.

Reaction can be carried in a variety of solvents as described above andat room temperature or at elevated temperature.

One embodiment relates to the modified polymer of the present inventionhas 1,4-cis content of 15 to 99%, or of 20 to 99%, or of 25 to 99%, orof 30 to 99%, or of 35 to 99%, or of 40 to 99%, or of 45 to 99%, or of50 to 99%, or of 55 to 99%, or of 60 to 99%, or of 65 to 99%, or of 70to 99%, or of 75 to 99%, or of 80 to 99%, or of 85 to 99%, or of 90 to99%, or of 95% to 99%.

Another embodiment relates to the modified polymer of the presentinvention has 1,4-cis content of 15 to 20%, or of 20 to 25%, or of 25 to30%, or of 30 to 35%, or of 35 to 40%, or of 40 to 45%, or of 45 to 50%,or of 50 to 55%, or of 55 to 60%, or of 60 to 65%, or of 65 to 70%, orof 70 to 75%, or of 75 to 80%, or of 80 to 85%, or of 85 to 90%, or of90 to 95%, or of 95% to 99%.

Another embodiment relates to the modified polymer of the presentinvention has more than 90% 1,4-cis content.

Another embodiment relates to the modified polymer of the presentinvention where the polymer is a polymer of 1,3-butadiene, isoprene,2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, or myrcene.Another embodiment relates to the modified polymer of the presentinvention where the polymer is a polymer of isoprene.

Another embodiment relates to modified polymer prepared according to anyof the methods described above.

Another aspect of the present invention relates to a compositioncomprising a modified polymer prepared according to any of the methodsdescribed above and a filler blended with the modified polymer.

Suitable fillers include carbon black and inorganic fillers, and thereinforcing filler is preferably at least one selected from the carbonblack and inorganic fillers.

Suitable inorganic fillers include silica, aluminum hydroxide, clay,alumina, talc, mica, kaolin, glass balloon, glass beads, calciumcarbonate, magnesium carbonate, magnesium hydroxide, calcium carbonate,magnesium oxide, titanium oxide, potassium titanate, and barium sulfate,and combinations thereof.

In one embodiment the filler is carbon black or silica.

Another aspect of the present invention relates to a rubber compositioncomprising a natural rubber; a modified polymer prepared according toany of the methods described above; and a filler.

The present invention may be further illustrated by reference to thefollowing examples.

EXAMPLES Example 1—Synthesis of 1,2-Bis(triethoxylsilyl)acetylene fromTriethoxychlorosilane

Freshly distilled trichloroethylene (from CaCl₂/Na₂CO₃; 1.4 mL, 15.7mmol) and Et₂O (15 mL) were cooled to −78° C. 2.5 M nBuLi in hexane(18.8 mL, 47.7 mmol) was added via an addition funnel. The funnel wasrinsed with THF (10 mL). After addition of nBuLi was complete, the whitesuspension was allowed to warm to ambient temperature, and the mixturewas stirred for 8 hours. The reaction mixture was then cooled to 0° C.,and ClSi(OEt)₃ (8 mL, 40.7 mmol) was added over 5 min. The mixture wasallowed to stir at ambient temperature for approximately 18 hours. Theprecipitate was removed by filtration and washed with Et₂O to provide apale yellow solution. The volatiles are removed under vacuum.(EtO)₃Si—C≡C—Si(OEt)₃ was purified by vacuum distillation (90-96° C. at0.1 mm Hg) to provide 3.85 g (11.0 mmol, 70% yield at >99% purity).

Example 2—Synthesis of 1,2-Bis(triethoxylsilyl)acetylene Using Acetyleneand Tetraethyl Orthosilicate (TEOS)

A three-neck round bottom flask was fitted with a gas bubbler, anaddition funnel, and a reflux condenser. A 3.0 M EtMgBr (20 mL, 60 mmol)solution in Et₂O was diluted with Et₂O (75 mL). During addition ofacetylene, evaporation of solvent occurred, so an additional 75 mL ofEt₂O were placed in the addition funnel; this additional solvent wasadded over the course of the reaction to maintain solvent volume. Thesolution was heated to a reflux, and then acetylene was bubbled throughthe refluxing solution for approximately 5 minutes and Et₂O was slowlyadded to the mixture. The reaction mixture was cooled to roomtemperature, and tetraethyl orthosilicate (TEOS; 13.5 mL, 60.6 mmol) wasadded. This mixture was heated at reflux for 18 hours. The mixture wasallowed to cool, filtered to remove the salts which were washed withEt₂O, to yield a pale yellow solution. Volatiles were removed undervacuum. (EtO)₃Si—C≡C—Si(OEt)₃ was purified by vacuum distillation (1.10g, 3.1 mmol, 5.2% yield at 96% purity; the yield can be improved withoptimization).

Example 3—General Synthesis

A two-necked round bottom flask was fitted with a reflux condenser andan addition funnel and charged with the appropriate alkyne and diethylether to generate ˜1.0 M solution. EtMgBr was added to the solution in adropwise fashion through the addition funnel at room temperature. Uponcompletion of the addition, the mixture was heated at reflux forapproximately 2 hours, and then the reaction was allowed to cool toambient temperature. TEOS was added via syringe at room temperature, andthe mixture was again heated at reflux for approximately 18 hours. Themixture was filtrated, and the salt precipitates were extracted withEt₂O. The volatile materials were removed under vacuum to provide acrude mixture of products, which were separated and isolated byfractional distillation.

Exemplary compounds prepared by this method are shown in Scheme 8.

Example 4—Polymerization of 1,3-Butadiene

Neodymium versatate (NdV4), triisobutyl aluminum (TBA),diisobutylaluminum hydride (DIBALH), and diisobutyl aluminum chloride(DIBAL-Cl) were 0.6, 8.9, 19.4 and 2.0 wt % of heptane solutionrespectively. The molar proportion of the each components was 1:20:10:2and catalyst level was 0.1 mmole of neodymium per 100 g of1,3-butadiene.

Neodymium versatate (NdV4) was prepared according to Kwag, “A HighlyReactive and Monomeric Neodymium Catalyst,” Macromolecules 35:4875-4879(2002), which is hereby incorporated by reference in its entirety.

Heptane (1800 g) was placed in oxygen and moisture free 5 L autoclavereactor filled with N₂ and brought to a desired temperature at around70° C. To the stirred heptane solution were added NdV4, butadiene, TIBA,DIBALH, and DIBAL-Cl, respectively. Then 1,3-butadiene (300 g) was addedto the stirred solution of reaction mixture and the polymerizationreaction was carried out at 70° C. for 2 hours. The polymerizationreaction was terminated by adding ethanol (1.5 g) and 6-di-tert-butyl4-methylphenol (1.5 g). The final product was dried in vacuo. Conversionwas calculated from the wt % of isolated polymer compared to the initialcharge of monomer. (conv. >95%).

Example 5—Preparation of Alkynylsilane End Terminated 1,4-Polybutadiene

NdV4, TIBA, DIBALH, and DIBAL-Cl were 0.6, 8.9, 19.4, and 2.0 wt % ofheptane solution, respectively. The molar proportion of the componentswas 1:20:10:2 and catalyst level was 0.1 mmole of neodymium per 100 g of1,3-butadiene.

Heptane (1800 g) was placed in in oxygen and moisture free 5 L autoclavereactor filled with N₂ and brought to a desired temperature at around70° C. To the stirred heptane solution, were added NdV4, butadiene,TIBA, DIBALH, and DIBAL-Cl, respectively. Then 1,3-butadiene (300 g) wasadded to the stirred solution of reaction mixture and the polymerizationreaction was carried out at 70° C. for 2 hours. Then, after addingalkynylsilane, 1,2-bis(triethoxylsilyl)acetylene dissolved in heptane(10 mL) (0.2 part by weight based on 100 parts by weight of butadiene)was added as an end terminating agent. The mixture was stirred at 70° C.for 1 hour. The polymerization reaction was terminated by adding ethanol(1.5 g) and 6-di-tert-butyl 4-methylphenol (1.5 g). The final productwas dried in vacuo. Conversion was calculated from the wt % of isolatedpolymer compared to the initial charge of monomer. (conv. >95%).

Example 6—Gel Permeation Chromatography (GPC) and Mooney ViscosityAnalysis

Molecular analysis was carried out with gel permeation chromatography(GPC). The results are shown in Table 1 and FIG. 1. Each GPC diagramresulted in distinct pattern showing a high molecular weight regionbecause alkynylsilane moieties were bound to polymer chain ends. Blueline is for 1,4-polybutadiene obtained in Example 4 and black line isfor alkynylsilane end terminated 1,4-polybutadiene obtained in Example5.

TABLE 1 MV (Mooney Mn Mn PDI Mz Mp viscosity) Example 4 263 578 2.2 1434423 32 Example 5 281 751 2.7 2663 417 38

Mooney viscosity analysis was carried out by rotary viscometer (AlphaTechnology, Mooney MV2000). High Mooney viscosity was obtained forpolymer obtained in Example 5, which was terminated with thealkynylsilanes. It was confirmed that high molecular weight region andmolecular weight distribution increased in the polymer obtained inExample 5 in GPC as a coupling reaction of alkynylsilane binding to1,4-polybutadiene chain ends.

Example 7—Measurement of Physical Properties of Rubber Compound

High cis-1,4-polybutadiene and end terminated high cis-1,4-polybutadiene(Examples 4 and 5, hereinafter referred to as BR) were mixed at 120° C.using a 500 cc Brabender according to the composition shown in Table 2below. The mixture was blended at 80° C. using a roll mill. Then, themixture was subjected to vulcanization at 160° C. using a press for atime period measured by RPA. And the measured physical properties areshown in Table 3 below. Physical properties increased with polymerobtained in Example 5 which was observed that abrasion (DIN), 100%, 300%modulus, tensile strength and elongation at break was improved comparedto polymer obtained in Example 4 due to alkynylsilane moieties bindingto polymer chain ends to assist to disperse silica fillers well duringrubber compound processing.

TABLE 2 Example 4 Example 5 SSBR (KKPC 5360H) 80.0 80.0 Example 1. 20.00 Example 2. 0 20.0 Silica (Uracil 7000GR ®) 80.0 80.0 Coupling agent(X50-S ®) 12.8 12.8 TDAE (rubber processing oil) 25.0 25.0 ZnO (zincoxide) 3.0 3.0 St-A (stearic acid) 2.0 2.0 6PPD(N-1,3-dimethylbutyl)-N-phenyl- 1.0 1.0 p-phenylenediamine) Sulfur 1.51.5 CBS (N-Cyclohexylbenzothiazol-2- 1.8 1.8 sulphenamide) DPG(1,3-Diphenylguanidine) 1.8 1.8 Unit: phr (part by weight based on 100parts by weight of rubber)

TABLE 3 Example 4 Example 5 Raw Mooney viscosity 32 38 Compound Mooneyviscosity 83.4 85.1 Hardness (Shore A) 75 75 Abrasion (DIN) 0.08730.0812 Tanδ at 0° C. 0.355 0.355 Tanδ at 60° C. 0.108 0.110 Tanδ at 70°C. 0.101 0.103 100% modulus (kgf/cm²) 35.9 38.1 300% modulus (kgf/cm²)145.8 150.1 Tensile strength (kgf/cm²) 169.3 192.4 Elongation at break(%) 340.6 383.9

Example 8—Polyisoprene Analyzed by DOSY NMR

Nd(O₂C₁₀H₁₉)₃(HO₂C₁₀H₁₉) (NdV4, 0.010 g, 0.011 mmol) was dissolved intoluene (1.00 mL) and transferred to a J-Young-style NMR tube equippedwith a Teflon valve. The aluminum alkyl reagents triisobutyl aluminum(TIBA, 0.014 mL, 0.059 mmol), diisobutyl aluminum hydride (DIBAL-H,0.006 mL, 0.034 mmol), and diisobutyl aluminum chloride (DIBAL-Cl, 0.003mL, 0.015 mmol) were added. The isoprene (0.120 g, 1.75 mmol) was thenadded and the J-Young tube was sealed. The reaction was heated at 60° C.for 90 min to consume the isoprene. (EtO)₃Si—C≡C—Si(OEt)₃ (0.041 g, 0.11mmol) was added to the toluene solution and reacted at 60° C. for 3hours. The polymeric product was precipitated by addition to methanol,isolated by filtration, and dried under vacuum. The resulting polymerwas analyzed by NMR.

In experiments when silylalkyne was added at ˜50% conversion of monomer,complete inhibition of polymerization was observed. This suggested thatthe alkyne binds active sites and inhibits polymerizations.

Example 9—DOSY Experimental Description

Samples were prepared by weighing 10-20 mg of polymer sample in a testtube and dissolving for 15 minutes in ˜0.6 mL CDCl₃. NMR experimentswere run on either Bruker DRX 400 MHz or Bruker avii 600 MHz instrument.For each experiment the D20 parameter was optimized to fit the gradientwindow of 2%-95% typically falling in the range of 0.05-0.15. In theexample shown in FIG. 2, the following optimized parameters were used:D20=0.70, ns=32, and 64 steps through gradient (D20 is the diffusiondelay parameter in the DOSY sequence). The signals in the range of ˜1.65ppm were identified as incorporated —Si(OEt)_(x) which diffused at thesame rate as the bulk polymer, suggesting covalent linking. This exampleshowed that (EtO)₃Si—C≡C—Si(OEt)₃ can be used as an end-groupfunctionalizing agent.

Example 10—Quenching Polyisoprene Reactions with Silylalkynes

Polymerizations of isoprene are carried out as shown below:

After completion of the polymerization silylalkyne of interest was addedand the polymer was analyzed by NMR characteristics such as ¹Hcorrelation (COSY, HSQC) and Diffusion based (DOSY) experiments (FIGS. 3and 4).

Results from these experiments showed evidence of (EtO)₃Si—C≡C—Si(OEt)₃bound to the bulk polymer sample. This evidence was supplied by thediffusion of peaks of interest matching that of the bulk polymersamples.

In experiments when silylalkyne was added at approximately 50%conversion of monomer complete inhibition of polymerization wasobserved. This suggested that the alkyne binds active sites and inhibitspolymerizations.

Example 11—Synthesis of Functionalized Dienes

The synthesis of functionalized dienes can be accomplished through avariety of methods; for example, Grignard reactions with chloroprene(Pidaparthi et al., “Preparation of 2-Trialkylsiloxy-Substituted1,3-Dienes and Their Diels-Alder/Cross-Coupling Reactions,” Org. Lett.9:1623-1626 (2007); Pidaparthi et al., “Preparation of2-Silicon-Substituted 1,3-Dienes and Their Diels-Alder/Cross-CouplingReactions,” J. Org. Chem. 74:8290-8297 (2009), which are herebyincorporated by reference in their entirety), E-H bond activation withene-ynes (Backvall et al., “Palladium-Catalyzed Regioselective Additionof Thiophenol to Conjugated Enynes. Efficient Syntheses of2-(Phenylsulfinyl) and 2-(Phenylsulfonyl) 1,3-Dienes,” J. Org. Chem.59:5850-5851 (1994), which is hereby incorporated by reference in itsentirety), reduction of 1,4-dichloro-2-X-2-butene (European PatentApplication No. 0154867 to Sato; European Patent Application No. 0189174to Sato et al.; Sato et al, “New Silane Coupling Agents with theButa-1,3-diene Moiety,” Chem. Ind. 20:743-744 (1984), which are herebyincorporated by reference in their entirety), or ene-yne metathesis(Junker et al, “Synthesis of 4-Aryl- and 4-Alkyl-2-silyl-1,3-butadienesand Their Diels-Alder/Cross-Coupling Reactions,” J. Org. Chem.75:8155-8165 (2010); Giessert et al., “Ethylene-Promoted IntermolecularEnyne Metathesis,” Org. Lett 5:3819-3822 (2003); Diver et al,“Metathesis,” Grela, Olefin Metathesis: Theory and Practice, John Wiley& Sons, pp. 153 (2014), which are hereby incorporated by reference intheir entirety) (Scheme 9). Precursors could also provide 2-substituteddienes, increasing the propensity for η⁴-coordination and 1,4-insertionsduring transition metal based coordination-polymerizations.

Example 12—Synthesis of 2-Silyl-Butadienes via Reduction of1,4-Dichloro-2-silyl-2-butenes

In the first step, the neat reaction was carried out in a flask with alarge head space and fitted with a reflux condenser due to the violentreflux observed after initiation of hydrosilylation, which was achievedby slowly raising the temperature to 35-45° C. This crude liquidhydrosilylation product was then added to a THF solution of ROH/Et₃N toyield 1,4-dichloro-2-silyl-2-butene compounds. After extraction fromammonium salts, compounds were isolated in ˜90% yields at 80-90% purity.The crude products were used further without further purification.

Reductions of the resulting functionalized alkenes were carried out inTHF at room temperature over 18-36 hours. The reaction worked mostefficiently with a ˜50:50 mixture of metallic zinc and powered zinc thatwas activated by washing with 6 M HCl (3×10 mL), water (5×10 mL), andethanol (3×5 mL) then dried at 120° C. under vacuum overnight. Aliquotsof the reaction mixture were taken periodically and reaction wasconsidered complete when the triplet (A) of the butene (FIG. 5) wasfully consumed. A quartet and two sets of doublets are characteristicsignals for the butadiene complexes followed during the reaction (FIG.5). When the zinc reductions stalled (i.e. conversion was slow orstopped) or white precipitate formed, additional THF was added to dilutethe reaction and solubilize ZnCl₂ from metallic zinc surfaces. Due tothe steric bulk the 2-(Me₂tBuOSi)-1,3-butadiene was of particularinterest and to the best of our knowledge has not been reported andcharacterized.

Silazane functionalized dienes were synthesized via the reductionmethod. The dichloro-butene compound containing the Si—NMe₂ functionalgroup was found to decompose quickly and reductions were carried out insitu. Likewise, the dichloro-butene compound containing the Si—NiPr₂functional group was found to decompose quickly and reductions werecarried out in situ. 2-(Me₂NMe₂Si)-1,3-butadiene was also found to bereactive, even when stored under a N₂ atmosphere at −40° C. ¹H NMR inbenzene-d₆ indicated that removal of the solvent under reduced pressureaccelerated decomposition (FIG. 6). In general, 2-silazido-butadienes ofthe type 2-(R₂N)R′₂Si—C₄H₅ are accessible via this method.

Example 13—Synthesis of Functionalized Dienes via Ruthenium CatalyzedEnyne Metathesis

Enyne metathesis reactions utilizing Hoveyda-Grubbs 2^(nd) Generationcatalyst and ethylene to obtain 2- and 2,3-substituted dienes weresuccessful in synthesizing compounds of interest. It was found thatindividual compounds required specific reaction conditions for optimizedyields. Optimized conditions for enyne metathesis reactions containingfunctional groups is shown in Scheme 10. For example, the internalalkyne nBu-CC—Si(OEt)₃ was converted to the 2,3-substituted butadienewith high conversions by intermolecular enyne metathesis under thereaction conditions of 1 mol % [Ru], 80 psi ethylene in methylenechloride at 60 C for 1 hour. More challenging terminal alkynes requiremore forcing conditions. To obtain complete conversion ofMe₂Si(NiPr₂)CCH to the corresponding 2-substituted diene, ethylenepressures of 40 bar and slow addition of catalyst were required toobtain acceptable conversions. In addition, intramolecular enynemetathesis generated 1,2-substituted dienes.

Example 14—Co-Polymerization with Isoprene

Functionalized monomers were tested for co-polymerization with isopreneby polymerizing isoprene using a neodymium verstate catalyst (NdV4) anda mixture of triisbutyl aluminum, diisobutyl aluminumhydride, anddiisobutyl aluminum chloride. Typically, these experiments wereperformed in the following manner: isoprene was polymerized understandard conditions (NdV4, TIBA, DIBALH, DIBAL-Cl, heptane) at roomtemperature for 1 hour (time required for full conversion of isoprene)to give polyisoprene. Next, the addition of the functionalized monomerwas added to the reaction mixture, stirred for an additional 1 hour, andthen the reaction mixture was quenched with methanol. The polymer wasisolated by precipitation and exhaustive washing.

Representative Example A

NdV4 (0.010 g, 0.011 mmol) was stirred with TIBA (0.022 g, 0.110 mmol),DIBAl—H (0.005 g, 0.033 mmol), and DIBAl—Cl (0.003 g, 0.017 mmol) in 0.6mL of benzene-d₆ for 5 minutes to generate a pale-teal solution.Isoprene (0.1 g, 1.5 mmol) was added to the solution in a J-young tubeand full conversion to polyisoprene was observed within 15 minutes atroom temperature. Crude, distilled 2-2-(iPr₂NMe₂Si)-1,3-butadiene ((˜0.1g, colorless liquid containing no [Ru]) was added to the reaction andheated at 60° C. for 1 hour. After this time, signals in the dieneregion of ¹H NMR spectrum were gone. The reaction mixture was quenchedwith methanol (1 mL) and dried overnight. Subsequent washing withmethanol and drying yielded the co-polymer material. ¹H NMR spectra and²⁹Si{¹H} HMBC experiments indicated the presence of polyisoprene with ¹HNMR peaks at 5.3, 2.2, 1.8 ppm and Si—Me signal at 0.3 ppm (FIGS. 7 and8). DOSY NMR of the co-polymer material indicated that Si—Me signal wascovalently attached to the polyiosprene polymer by matching diffusionrates (FIG. 9).

Representative Example B

NdV4 (0.020 g, 0.023 mmol) was stirred with TIBA (0.090 g, 0.920 mmol),DIBAl—H (0.016 g, 0.115 mmol), and DIBAl—Cl (0.006 g, 0.035 mmol) inheptane (20 mL) for 15 minutes to generate a pale-teal solution.Isoprene (1 g, 15 mmol) was added to the solution, and the reactionmixture was stirred for 1 hour. Then, a crude mixture of2-(Me₂NMe₂Si)-1,3-butadiene in toluene (˜0.3 g in a 3 mL solution alsocontaining deactivated [Ru] catalyst) was added to the reaction mixture,and the mixture was stirred for 1 hour. Methanol was added to quench thepolymerization and precipitate the co-polymer. The precipitated polymerwas washed with methanol (10×5 mL) to remove small-molecule impurities.¹H NMR spectra of the polymer contained upfield SiMe signals, and²⁹Si{¹H} HMBC experiment showed correlations between Si centers andmethyl groups. On the basis of the extensive washing and presence ofSiMe signals (FIGS. 10 and 11), we conclude that SiMe groups arecovalently bonded to the polyisoprene (end functionalization). TheSi—N(iPr)₂ were hydrolyzed during work up in methanol, and the ¹H NMRsignal at 3.02 ppm was assigned to a Si—OMe end functional group. DOSYNMR of the material shows peaks associated with polyisoprene (5.3, 2.2,and 1.8 ppm) diffused together as well as peaks containing SiMe signalsin the range of 0.0-0.3 ppm (FIG. 12).

Although preferred embodiments have been depicted and described indetail herein, it will be apparent to those skilled in the relevant artthat various modifications, additions, substitutions, and the like canbe made without departing from the spirit of the invention and these aretherefore considered to be within the scope of the invention as definedin the claims which follow.

What is claimed:
 1. A modified polymer having the structure of Formula(I):

wherein

is a polymer; A is selected from the group consisting of

C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, arylene, and

wherein C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, and arylenecan be optionally substituted from 1 to 4 times with a substituentindependently selected from the group consisting of H, halogen, C₁₋₆alkyl, and —NR⁷R⁸;

is a point of attachment of A to

group; R¹ is C₁₋₆ alkyl; R² is H or C₁₋₆ alkyl; R³ is H or C₁₋₆ alkyl;R⁴ is C₁₋₆ alkyl; R⁵ is H or C₁₋₆ alkyl; R⁶ is H or C₁₋₆ alkyl; R⁷ is Hor C₁₋₆ alkyl; R⁸ is H or C₁₋₆ alkyl; R⁹ is C₁₋₆ alkyl; R¹⁰ is C₁₋₆alkyl; X¹ is C₁₋₆ alkylene; X² is C₁₋₁₅ alkylene; Y is O or N; Z is H,R⁹, or Si(R¹⁰)₃; a is 0 to 2; b is 1 or 2; and n is 1 to
 3. 2. Themodified polymer of claim 1, wherein the polymer of Formula (I) hasFormula (Ia):

wherein A is selected from the group consisting of

C₁₋₁₅ alkyl, C₃₋₈ cycloalkyl, and aryl, wherein C₁₋₁₅ alkyl, C₃₋₈cycloalkyl, and aryl can be optionally substituted from 1 to 4 timeswith a substituent independently selected from the group consisting ofH, halogen, C₁₋₆ alkyl, and —NR⁷R⁸.
 3. The modified polymer of claim 2having the structure:


4. The modified polymer of claim 2 having the structure:


5. The modified polymer of claim 1, wherein the polymer

has a 1,4-cis content of 15 to 99%.
 6. The modified polymer of claim 1,wherein the polymer

is a polymer of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene,1,3-pentadiene, 1,3-hexadiene, or myrcene.
 7. The modified polymer ofclaim 1, wherein the polymer

is a polymer of isoprene.
 8. A process for polymerizing unsaturatedhydrocarbon monomers, said process comprising: providing unsaturatedhydrocarbon monomers; providing a compound of Formula (II):

wherein A is selected from the group consisting of

C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, arylene, and

wherein C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, and arylenecan be optionally substituted from 1 to 4 times with a substituentindependently selected from the group consisting of H, halogen, C₁₋₆alkyl, and —NR⁷R⁸;

is a point of attachment of A to

group; R¹ is C₁₋₆ alkyl; R² is H or C₁₋₆ alkyl; R³ is H or C₁₋₆ alkyl;R⁴ is C₁₋₆ alkyl; R⁵ is H or C₁₋₆ alkyl; R⁶ is H or C₁₋₆ alkyl; R⁷ is Hor C₁₋₆ alkyl; R⁸ is H or C₁₋₆ alkyl; R⁹ is C₁₋₆ alkyl; R¹⁰ is C₁₋₆alkyl; X¹ is C₁₋₆ alkylene; X² is C₁₋₁₅ alkylene; Y is O or N; Z is H,R⁹, or Si(R¹⁰)₃; a is 0 to 2; b is 1 or 2; n is 1 to 3; and providing acatalyst selected from the group consisting of: (1) a mixture of (A) acompound of Formula M¹A¹ ₃; (B) a halogen containing compound; and (C)an organometallic compound, wherein M¹ is a lanthanide metal; A¹ isC₈₋₂₀ carboxylate; (2) a mixture of (A) a compound of Formula M²(HA²)A²₃; (B) a halogen containing compound; and (C) an organometalliccompound, wherein M² is a lanthanide metal; A² is C₈₋₂₀ carboxylate; (3)a compound of Formula Li-Alk, wherein Alk is C₁₋₆ alkyl; and (4) acompound of Formula (III): MC(SiHAlk₂)₃(R¹¹)₂ (III), wherein M is alanthanide or a transition metal; Alk is C₁₋₆ alkyl; R¹¹ is halide,bis(oxazolinato), carboxylate, acetyl acetonate, amidate, alkoxide,amide, BR¹² ₄, AlR¹² ₄, or alkyl aluminate; R¹² is independentlyselected at each occurrence thereof from the group consisting of H,C₆F₅, phenyl, and C₁₋₆ alkyl; and polymerizing the unsaturatedhydrocarbon monomers in the presence of the catalyst and the compound ofFormula (II) under conditions effective to produce the modified polymer.9. The process of claim 8, wherein the catalyst is a mixture of (A) acompound of Formula M¹A¹ ₃; (B) a halogen containing compound; and (C)an organometallic compound, wherein M¹ is a lanthanide metal; A¹ isC₈₋₂₀ carboxylate.
 10. The process of claim 8, wherein the catalyst is amixture of (A) a compound of Formula M²(HA²)A² ₃; (B) a halogencontaining compound; and (C) an organometallic compound, wherein M² is alanthanide metal; A² is C₈₋₂₀ carboxylate.
 11. The process of claim 8,wherein the catalyst is a compound of Formula Li-Alk, wherein Alk isC₁₋₆ alkyl.
 12. The process of claim 8, wherein the catalyst is acompound of Formula (III): MC(SiHAlk₂)₃(R¹¹)₂ (III), wherein M is alanthanide or a transition metal; Alk is C₁₋₆ alkyl; R¹¹ is halide,bis(oxazolinato), carboxylate, acetyl acetonate, amidate, alkoxide,amide, BR¹² ₄, AlR¹² ₄, or alkyl aluminate; R¹² is independentlyselected at each occurrence thereof from the group consisting of H,C₆F₅, phenyl, and C₁₋₆ alkyl.
 13. The process of claim 8, wherein thecompound of Formula (II) has Formula (IIa):

wherein A is selected from the group consisting of

C₁₋₁₅ alkyl, C₃₋₈ cycloalkyl, and aryl, wherein C₁₋₁₅ alkyl, C₃₋₈cycloalkyl, and aryl can be optionally substituted from 1 to 4 timeswith a substituent independently selected from the group consisting ofH, halogen, C₁₋₆ alkyl, and —NR⁷R⁸.
 14. The process of claim 13, whereinthe compound of Formula (IIa) has the following structure:


15. The process of claim 13, wherein the compound of Formula (IIa) hasthe following structure:


16. The process of claim 8, wherein the modified polymer has 1,4-ciscontent of 15 to 99%.
 17. The process of claim 8, wherein the modifiedpolymer has more than 90% cis-content.
 18. The process of claim 8,wherein the modified polymer has a Mooney viscosity of 10 to
 100. 19. Aprocess for producing a modified polymer, said process comprising:providing a polymer; providing a compound of Formula (II):

wherein A is selected from the group consisting of

C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, arylene, and

wherein C₁₋₁₅ alkyl, C₁₋₁₅ alkylene, C₃₋₈ cycloalkyl, aryl, and arylenecan be optionally substituted from 1 to 4 times with a substituentindependently selected from the group consisting of H, halogen, C₁₋₆alkyl, and —NR⁷R⁸;

is a point of attachment of A to

group; R¹ is C₁₋₆ alkyl; R² is H or C₁₋₆ alkyl; R³ is H or C₁₋₆ alkyl;R⁴ is C₁₋₆ alkyl; R⁵ is H or C₁₋₆ alkyl; R⁶ is H or C₁₋₆ alkyl; R⁷ is Hor C₁₋₆ alkyl; R⁸ is H or C₁₋₆ alkyl; R⁹ is C₁₋₆ alkyl; R¹⁰ is C₁₋₆alkyl; X¹ is C₁₋₆ alkylene; X² is C₁₋₁₅ alkylene; Y is O or N; Z is H,R⁹, or Si(R¹⁰)₃; a is 0 to 2; b is 1 or 2; n is 1 to 3; and reacting thepolymer with the compound of Formula (II) under conditions effective toproduce the modified polymer.
 20. The process of claim 19, wherein thecompound of Formula (II) has Formula (IIa):

wherein A is selected from the group consisting of

C₁₋₁₅ alkyl, C₃₋₈ cycloalkyl, and aryl, wherein C₁₋₁₅ alkyl, C₃₋₈cycloalkyl, and aryl can be optionally substituted from 1 to 4 timeswith a substituent independently selected from the group consisting ofH, halogen, C₁₋₆ alkyl, and —NR⁷R⁸.
 21. The process of claim 20, whereinthe compound of Formula (IIa) has the following structure:


22. The process of claim 20, wherein the compound of Formula (Ia) hasthe following structure:


23. The process of claim 19, wherein the polymer has a 1,4-cis contentof 15 to 99%.
 24. The process of claim 19, wherein the polymer is apolymer of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene,1,3-pentadiene, 1,3-hexadiene, or myrcene.
 25. The process of claim 19,wherein the polymer is a polymer of isoprene.
 26. A modified polymerprepared by the process of claim
 19. 27. A composition comprising: amodified polymer prepared according to claim 19 and a filler blendedwith said modified polymer.
 28. The composition of claim 19, wherein thefiller is carbon black or silica.
 29. A rubber composition comprising: anatural rubber; a modified polymer prepared by the process of claim 19;and a filler.
 30. A process for polymerizing unsaturated hydrocarbonmonomers, said process comprising: providing unsaturated hydrocarbonmonomers; providing a compound of Formula (V):

wherein R is H or C₁₋₆ alkyl; R′ is selected from the group consistingof H, C₁₋₆ alkyl, —OC₁₋₆ alkyl; and —NR^(a)R^(b); R″ is H or C₁₋₆ alkyl;R^(a) is H or C₁₋₆ alkyl; R^(b) is H or C₁₋₆ alkyl; and x is 0 to 3; andproviding a catalyst which is a mixture of (A) a compound of FormulaM²(HA²)A² ₃; (B) a halogen containing compound; and (C) anorganometallic compound, wherein M² is a lanthanide metal; A² is C₈₋₂₀carboxylate; and polymerizing the unsaturated hydrocarbon monomers inthe presence of the catalyst and the compound of Formula (V) underconditions effective to produce the modified polymer.
 31. A process forpolymerizing unsaturated hydrocarbon monomers, said process comprising:providing unsaturated hydrocarbon monomers; providing a compound ofFormula (V):

wherein R is H or C₁₋₆ alkyl; R′ is selected from the group consistingof H, C₁₋₆ alkyl, —OC₁₋₆ alkyl; and —NR^(a)R^(b); R″ is H or C₁₋₆ alkyl;R^(a) is H or C₁₋₆ alkyl; R^(b) is H or C₁₋₆ alkyl; and x is 0 to 3; andproviding, as a catalyst, a compound of Formula (III):MC(SiHAlk₂)₃(R¹¹)₂ (III), wherein M is a lanthanide or a transitionmetal; Alk is C₁₋₆ alkyl; R¹¹ is halide, bis(oxazolinato), carboxylate,acetyl acetonate, amidate, alkoxide, amide, BR¹² ₄, AlR¹² ₄, or alkylaluminate; R¹² is independently selected at each occurrence thereof fromthe group consisting of H, C₆F₅, phenyl, and C₁₋₆ alkyl; andpolymerizing the unsaturated hydrocarbon monomers in the presence of thecatalyst and the compound of Formula (V) under conditions effective toproduce the modified polymer.